A. Technical Field
The present invention relates to a process for producing a (meth)acrylic ester which uses an ion-exchange resin as a catalyst.
B. Background Art
An ion-exchange resin which has been so far used as a catalyst when a (meth)acrylic ester is produced from raw materials of an alcohol and an acid is often marketed in a moistened condition with water. When the ion-exchange resin is used in a reaction, water is usually projected into a reaction vessel in advance so as to prevent the damage of the resin. Then, the water is drained outside the reaction vessel after the ion-exchange resin is projected, so that the ion-exchange resin is packed in the reaction vessel.
However, an esterification reaction is an equilibrium reaction. Therefore, if water exists in a system of reaction, a conversion rate is low and a reaction is difficult to proceed. Therefore, the problem arises that the more water content the ion-exchange resin used as a catalyst in the esterification reaction contains, the more greatly a reaction yield falls. Accordingly, it is desired that the water content contained in the ion-exchange resin should be decreased as much as possible, before the ion-exchange resin is used in the esterification reaction.
Furthermore, a reaction to produce a hydroxyalkyl (meth)acrylate among the (meth)acrylic ester from raw materials of the alkylene oxide and the acid is not an equilibrium reaction. However, in the case where the ion-exchange resin is used as a catalyst of the esterification reaction, the more water the ion-exchange resin contains, the more greatly the concentration of raw materials in a system of reaction and a reaction yield falls. Accordingly, it is desired that the water content contained in the ion-exchange resin should be decreased as much as possible.
The decrease of water content contained in the ion-exchange resin has so far been performed by methods such as azeotropic dehydration by use of a solvent, warming under reduced pressure, and washing by use of a polar solvent.
However, if the effective utilization of a distillate as formed on the occasion of azeotropic dehydration is taken into account, it is preferred that such a solvent as forms a binary liquid phase with water is used, and that an oil phase separated from a water phase is recycled as a reflux. However, in the case where azeotropic distillation is performed with a stirred tank apparatus by use of an water-insoluble solvent, the ion-exchange resin tends to aggregate in the solvent, and in its turn an operational problem, such as a difficulty in stirring, tends to arise.
A. Objects of the Invention
An object of the present invention is to provide a process for producing a (meth)acrylic ester which enables to obtain a (meth)acrylic ester in an excellent reaction yield.
B. Disclosure of the Invention
The present inventors studied and studied with encouragement to themselves and great efforts to solve the above problems. As a result, the inventors have completed the present invention by finding out that in the case of the production of the (meth)acrylic ester, prior to performing an esterification reaction step, it becomes possible to improve a yield remarkably in the esterification reaction by performing a dehydration step of removing water impregnated in an ion-exchange resin by use of an alcohol and/or an acid of raw materials in an esterification reaction and/or the resulting ester in the esterification reaction.
Furthermore, the inventors have completed the present invention by finding out that in the case of the production of the (meth)acrylic ester from raw materials of the alkylene oxide and the acid, it becomes possible to prevent the aggregation of the ion-exchange resin on the occasion of dehydration by azeotropic removal of water as contained in the ion-exchange resin by using a solvent which not only forms a binary liquid phase with water but also has a constant solubility to water, and that it becomes possible to decrease effectively the water content as contained in the ion-exchange resin.
That is to say, the primary process for producing a (meth)acrylic ester according to the present invention is a process which uses an alcohol and an acid as raw materials and an ion-exchange resin as a catalyst, and the process is characterized by comprising a dehydration step and an esterification step, wherein the esterification reaction step follows the dehydration step in which water impregnated in the ion-exchange resin is removed by using as a dehydrating solvent at least one member selected from the group consisting of the alcohol, the acid, and the resulting ester.
Furthermore, the second process for producing a (meth)acrylic ester according to the present invention is a process which uses an alkylene oxide and an acid as raw materials and an ion-exchange resin as a catalyst, and the process is characterized by comprising a dehydration step and an esterification step, wherein the esterification reaction step follows the dehydration step in which water impregnated in the ion-exchange resin is azeotropically dehydrated by distilling a solvent (A) together with the ion-exchange resin, wherein the solvent (A) exhibits a solubility of not less than 0.05 g per 100 g of water at 20xc2x0 C., and forms a binary liquid phase with water.
Furthermore, the third process for producing a (meth)acrylic ester according to the present invention is a process which uses an alkylene oxide and an acid as raw materials and an ion-exchange resin as a catalyst, and the process is characterized by comprising a dehydration step and an esterification step, wherein the esterification reaction step follows the dehydration step in which water impregnated in the ion-exchange resin is azeotropically dehydrated by distilling a solution of a mixture of solvents (B) and (C) together with the ion-exchange resin, wherein the solvent (B) is soluble in water in arbitrary ratio and wherein the solvent (C) exhibits a solubility of less than 0.05 g per 100 g of water at 20xc2x0 C. and forms a binary liquid phase with water.
These and other objects and the advantages of the present invention will be more fully apparent for the following detailed disclosure.
Modes for carrying out the present invention are hereinafter described in detail.
In a process for producing a (meth)acrylic ester of the present invention, prior to an esterification reaction step, it is important to perform a dehydration step to remove water impregnated in an ion-exchange resin used as a catalyst. In the dehydration step, it becomes possible to improve a yield in the esterification reaction following the dehydration step by decreasing the water content in the ion-exchange resin sufficiently in advance in the dehydration step.
In the present invention, the aforementioned dehydration step is a step of removing water impregnated in the ion-exchange resin by using as a dehydrating solvent at least one member selected from the group consisting of an alcohol, an acid (raw materials of the esterification reaction), and the resulting ester in the esterification reaction. In the case where the dehydrating solvent remains in the ion-exchange resin after dehydration, it becomes possible to improve a reaction yield effectively without preventing the esterification reaction by using as dehydrating solvents raw materials of the esterification reaction, or the resulting ester in the esterification reaction.
In the aforementioned dehydration step, a method of removing water impregnated in the ion-exchange resin is not especially limited except for using the aforementioned dehydrating solvent. For example, a method of washing the ion-exchange resin with the aforementioned solvent, a method of removing water by performing distillation after adding the aforementioned solvent to the ion-exchange resin or such is preferably enumerated.
In the case of the method of washing the ion-exchange resin with the aforementioned solvent, more specifically in the case of washing by use of a fixed-bed reactor, it is better that water of the ion-exchange resin is removed by allowing the water to pass spaces between the resins which is packed by projecting continuously the aforementioned dehydrating solvent into a reaction vessel after the ion-exchange resin is packed in the reaction vessel. It is preferred that the aforementioned dehydrating solvent is beforehand warmed, or that the reaction vessel is beforehand warmed by use of a heat resource such as steam. In this case, warming temperature is preferably in the approximate range from 30 to 120xc2x0 C. Furthermore, in the case of washing by use of a stirred tank reactor, it is better that water content of the ion-exchange resin is removed by repeating such a similar operation as is to extract out only a liquid in a reaction vessel and to project the further dehydrating solvent again after projecting the ion-exchange resin and the aforementioned dehydrating solvent into the reaction vessel and stirring them for a constant period of time, or by projecting the aforementioned dehydrating solvent into the reaction vessel continuously with keeping a liquid volume in the reaction vessel constant. A method of washing the ion-exchange resin with the solvent is preferably a method of washing by use of the aforementioned fixed-bed reactor. In addition, it is desired that washing should be carried out so that the concentration of water content in liquid wastes after washing can be not more than 10 weight %, preferably not more than 5 weight %.
In the case of the aforementioned method of removing water by performing distillation after adding the solvent to the ion-exchange resin, more specifically, it is better that water content of the ion-exchange resin is removed by projecting the solvent and the ion-exchange resin into a reaction vessel to prepare a slurry state liquid, heating the liquid with stirring, and distilling the liquid. Especially, in the case where the used dehydrating solvent forms an azeotropic composition with water, azeotropic dehydration is preferable.
In the case of producing a (meth)acrylic ester from an alkylene oxide and an acid as raw materials, water impregnated in an ion-exchange resin is azeotropically dehydrated by distilling a solvent (A) together with the ion-exchange resin. In this case, the aforementioned solvent (A) is such a solvent as not only has the solubility of not less than 0.05 g per 100 g of water at 20xc2x0 C., but also forms a binary liquid phase with water. The formation of a binary liquid phase between the solvent (A) and water enables to remove water content from the ion-exchange resin by azeotropic dehydration. Besides the solvent (A) having the solubility of not less than 0.05 g per 100 g of water at 20xc2x0 C. enables to prevent the aggregation of the ion-exchange resin on the occasion of dehydration.
The aforementioned solvent (A) is not especially limited, as long as the solvent has not only the solubility of not less than 0.05 g per 100 g of water at 20xc2x0 C., but also the solubility to such a degree as does not prevent the solvent from forming a binary liquid phase with water. Examples thereof include butanol, pentanol, hexanol, heptanol, octanol, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl acrylate, nitrobenzene, cyclohexanol, methyl isobutyl ketone, isobutyl acetate, and the like. They may be used alone or in combination of two or more.
In the case of producing a (meth)acrylic ester from an alkylene oxide and an acid as raw materials, it is better that water impregnated in an ion-exchange resin is azeotropically dehydrated by distilling a solution of a mixture of solvents (B) and (C) together with the ion-exchange resin. The aforementioned solvent (B) is a solvent which is soluble in water in arbitrary ratio, and the aforementioned solvent (C) is a solvent which not only has the solubility of less than 0.05 g per 100 g of water at 20xc2x0 C., but also forms a binary liquid phase with water. The solvent (C) in the mixture solution having the solubility of only less than 0.05 g per 100 g of water at 20xc2x0 C. and the formation of a binary liquid phase with water enables to remove water content from the ion-exchange resin by azeotropic dehydration. Besides the solvent (B) in the mixture solution having the solubility to such a degree as is soluble in water enables to prevent the aggregation of the ion-exchange resin on the occasion of dehydration.
The aforementioned solvent (B) is not especially limited, as long as the solvent is soluble in water in arbitrary ratio. Examples thereof include methanol, ethanol, 1-propanol, 2-propanol, formic acid, acetic acid, propanoic acid, butanoic acid, (meth)acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acetonitrile, acetone, monoethanol amine, diethanol amine, triethanol amine, glycerin, monoethylene glycol, diethylene glycol, triethylene glycol, and the like. They may be used alone or in combination of two or more. For example, in the case of using the ion-exchange resin after dehydration in the production of a hydroxyalkyl (meth)acrylate, using (meth)acrylic acid as the solvent (B) is preferable, because the (meth)acrylic acid is a raw material of the hydroxyalkyl (meth)acrylate and the ion-exchange resin is available for a reaction as it is, although the (meth)acrylic acid is attached to the ion-exchange resin after dehydration treatment.
The aforementioned solvent (C) is not especially limited, as long as the solvent is such a solvent as has not only the solubility of only less than 0.05 g per 100 g of water, but also the solubility to such a degree as does not prevent the formation of a binary liquid phase with water. Examples thereof include toluene, benzene, o-xylene, m-xylene, p-xylene, heptane, hexane, octane, cyclohexane, and the like. They may be used alone or in combination of two or more.
A mixing ratio between the aforementioned solvents (B) and (C) is preferably (B)/(C)=0.1-50 (volume ratio). When the mixing ratio is above this ratio, a condensate of vapor arising from azeotropic dehydration does not form a binary liquid phase with water, and the amount of the solvent (B) in wasted water becomes large to increase loss of the solvent (B). On the other hand, when the mixing ratio is below this ratio, the ion-exchange resin is easy to aggregate, so that the mixing ratio either above or below this ratio is disadvantageous.
Heating temperature, heating time and such are appropriately established according to a boiling point of the used solvent or such, and they are not especially limited. Heating temperature is preferably in the approximate range from 30 to 120xc2x0 C., and heating time is preferably in the approximate range from 2 to 24 hours. A method of dehydrating the ion-exchange resin by distilling may be performed with any apparatus, as long as the method is a stirred tank reaction form. Especially, it is preferred that the method is performed with a stirred tank reactor combined with a distillation column. Furthermore, it is desired that distillation should be carried out until the amount of water content calculated on the amount of water content contained in the ion-exchange resin before dehydration and the amount of the packed ion-exchange resin is distilled out as a water phase, or that distillation should be carried out until the temperature reaches to such a temperature as makes the concentration of water content in a reaction vessel an aimed concentration (usually not more than 5 weight %), because the correlation between the concentration of water content and the temperature in the reaction vessel is found out if the condition of pressure is determined according to the used dehydrating solvent.
In the present invention, the aforementioned dehydration step is preferably carried out under reduced pressure. Especially, in the case where the aforementioned dehydration step is carried out by a method of removing water by performing distillation after adding the dehydrating solvent to the ion-exchange resin, distilling under reduced pressure is effective, because distilling under reduced pressure promotes dehydration. Above all, in the case where the aforementioned terminal temperature of distillation exceeds 120xc2x0 C. on the occasion of dehydration by distilling, the dehydration step is more preferably performed under reduced pressure. The reduced pressure in reducing pressure is not especially limited, but it is preferably in the range from 30 to 700 hPa, more preferably from 50 to 300 hPa.
In the present invention, it is preferred that the dehydrating solvent is recovered from liquid wastes that are generated in the aforementioned dehydration step and contain water and the dehydrating solvent, and that the solvent is recycled in the dehydration step and/or the esterification reaction step. Specifically, in the case of the method of washing the ion-exchange resin with the aforementioned solvent, it is better that the aforementioned dehydrating solvent contained in liquid wastes is separated from water by distilling the liquid wastes after washing. In the case of the method of performing distillation after adding the aforementioned dehydrating solvent to the ion-exchange resin, it is better that after a generating vapor is condensed with a condenser, the resulting condensate is separated into a liquid of a water phase and an oil phase, and that the oil phase is returned into a reaction vessel as the dehydrating solvent. Furthermore, as to the dehydrating solvent dissolving in the water phase, it is better that the solvent is further separated and recovered by an operation such as distillation, and that the solvent is recycled in the dehydration step and/or the esterification reaction step. Incidentally, it is preferred that an operation of distilling liquid wastes for reuse, an operation of condensing and separating liquid wastes or such is performed with the aforementioned dehydration step at the same time, and that the solvent is recycled at any time.
In the aforementioned dehydration step, it is better that the solvent is used so that a use ratio between the ion-exchange resin and the aforementioned dehydrating solvent, a ratio of the dehydrating solvent to the volume of the ion-exchange resin in a moistened condition with water can be 1 to 30 times amount (volume), more preferably 5 to 20 times amount (volume). If the dehydrating solvent is above 30 times amount (volume), dehydration time lengthens and it is disadvantageous economically. Below 1 times amount (volume), the efficiency of dehydration falls and as a result, the esterification reaction yield falls, so that the volume of the ion-exchange resin above 30 times amount or below 1 times amount is disadvantageous.
In the aforementioned dehydration step, it is preferred that dehydration is performed until the concentration of water content in a reaction vessel packed with the ion-exchange resin becomes not more than 5 weight %. If the concentration of water content is within the aforementioned range, it becomes possible to improve a yield sufficiently without inhibiting the esterification reaction. The measurement of the water content concentration can be carried out, for example, by a method as described in the portion hereof under the heading of xe2x80x9cDETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSxe2x80x9d.
A process for producing a (meth)acrylic ester of the present invention is a process in which the esterification reaction step following the aforementioned dehydration step is performed. In the esterification reaction step, an alcohol or an alkylene oxide, and an acid are used as raw materials and an ion-exchange resin is used as a catalyst.
As the acid, a raw material in the aforementioned esterification reaction, acrylic acid or methacrylic acid is enumerated. They may be used alone or in combination of two.
The alcohol, a raw material in the aforementioned esterification reaction is not especially limited. For example, saturated or unsaturated fatty alcohol having 1 to 12 carbon atoms, fatty cyclic alcohol having 3 to 10 carbon atoms, aromatic alcohol having 6 to 10 carbon atoms or such is enumerated. Especially, fatty alcohol or fatty cyclic alcohol having 1 to 12 carbon atoms is preferably used. Examples thereof include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, isononyl alcohol, lauryl alcohol, and the like. They may be used alone or in combination of two or more.
The alkylene oxide, a raw material in the aforementioned esterification reaction, is not especially limited. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and the like. They may be used alone or in combination of two or more.
The ion-exchange resin to be used in the present invention is not especially limited. For example, all usually marketed ion-exchange resins such as gel type, porous type, and high-porous type are effective. These ion-exchange resins may be used alone or in combination of two or more.
In the present invention, various conditions such as a concrete method of the esterification reaction step and reaction temperature are appropriately established, and they are not especially limited. It is preferred that in the esterification reaction step, the acid, and the alcohol or the alkylene oxide, raw materials, are projected after the end of the aforementioned dehydration step to start the esterification reaction.
In the present invention, it is preferred that the aforementioned dehydration step is performed by using a reaction vessel of a reaction apparatus with which the aforementioned esterification reaction step will be performed. It becomes possible to perform the both steps continuously by carrying out in this manner the dehydration step with the reaction vessel of the apparatus used for the esterification reaction, so that it becomes possible to produce the (meth)acrylic ester with good workability.
(Effects and Advantages of the Invention)
The present invention enables to produce a (meth)acrylic ester in an excellent yield.
Examples and comparative examples according to the present invention are hereinafter illustrated. However, the present invention is not limited thereto.
Incidentally, the concentration of water content, the water content of an ion-exchange resin, and the conversion rate of acrylic acid were measured by the following methods.
(Concentration of water content)
The concentration of water content was measured by use of Karl-Fischer moisture meter (produced by KYOTO ELECTRONICS MANUFACTURING CO., LTD.; model MKS-1s).
(Water content (the concentration of water content) of an ion-exchange resin)
The water content of an ion-exchange resin was measured by Karl-Fischer method.
(Conversion rate of acrylic acid)
The concentration (X) of acrylic acid in a raw material liquid provided for a reaction vessel in the esterification reaction step and the concentration (Y) of acrylic acid in a reaction liquid after the end of the esterification reaction were respectively measured by acid content titration, and the conversion rate of acrylic acid was calculated according to the following equation:
The conversion rate of acrylic acid (%)=(Xxe2x88x92Y)/Xxc3x97100 